Transient absorption (TA) measurements on nanosecond through microsecond time scales were performed on solutions of tris(2,2'-bipyridine)ruthenium(II) and anthracene in various relative concentrations. Following energy transfer from the ruthenium trisbipyridine sensitizer, the anthracene acceptor undergoes dimerization, which has been shown to occur via triplet-triplet annihilation. Values of the associated rate constants were determined by fitting the experimental TA data to the nonlinear kinetic model implied by the law of mass action. We report values of 6.9 × 108 liter mol−1 s−1 and 7.9 × 109 liter mol−1 s−1, respectively, for the rate constants for energy transfer and for anthracene dimerization.
We exploit the strong spin-orbit coupling in iridium to modify the linear absorption spectrum of a novel iridium(III) complex so as to broaden the spectral region over which it exhibits reverse saturable absorption. We discuss the design of the new chromophore, present its ground-state absorption spectrum, and report values of its singlet excited-state lifetime and singlet and triplet excited-state absorption cross sections, determined from femtosecond transient difference absorption measurements and nanosecond and picosecond open-aperture Z scans.
Experimental measurements were performed to completely characterize the linear and nonlinear optical properties in butyl salicylate solution of a novel bipyridyl platinum(II) complex bearing benzothiazolylethynylfluorene ligands. This paper describes the analysis of the resulting experimental data and reports the values of the ground- and excited-state absorption cross sections and of the other photophysical parameters characterizing the chromophore/solvent system.
In top-hat Z scans that employ tunable sources such as optical parametric generators without line-narrowing gratings, the size of the aperture used to clip the beam may exceed the coherence length, and the variation with z of the transverse profile of the resulting partially coherent beam may differ significantly from that of a perfect top-hat beam. After a careful validation of our experimental set-up, we perform picosecond open-aperture Z scans with a top-hat beam at selected wavelengths in the visible and nanosecond open-aperture Z scans with a spatially Gaussian beam at 532-nm wavelength on a toluene solution of a particular platinum(II) 2,2′-bipyridyl complex bearing naphthalimidylethynyl-substituted fluorenylacetylide ligands. We report values of the singlet and triplet excited-state absorption cross sections of the complex.
We report the results of measurements performed on a particular platinum(II)
4,4'-bis[3-ethyl-1-(2-ethylhexyl)heptyl]-2,2'-bipyridyl complex bearing 2-(benzothiazol-2'-yl)-7-ethynyl-9,9-dihexadecyl-fluorenyl units. A similar complex,
identical except for the presence of ethyl groups at the 9-position of the fluorenes and tert-butyl groups at the 4- and
4'- positions of the bipyridine, was recently reported to possess a very high ratio of triplet excited-state absorption to
ground-state absorption, a quantity that has long been used as a figure of merit for reverse saturable absorbers; in
addition, femtosecond transient difference absorption experiments and picosecond open-aperture Z-scans have shown it
to display broad nonlinear absorption throughout the visible spectrum. In this work, we measured the triplet excitedstate
absorption cross section at several representative wavelengths between 450 nanometers and 660 nanometers in an
open-aperture top-hat Z-scan experiment employing a
nanosecond-pulsed tunable optical parametric oscillator (OPO).
The open-aperture Z-scan is a highly sensitive single-beam experiment used to measure nonlinear absorption. Since the
spatial profile of the OPO beam resembled a cross-pattern, we closed an adjustable iris on the beam to create a top-hat
profile. A dynamic five-level model was used to fit the Z-scan data.
Current interest in nanophotonics has spurred the synthesis of a variety of molecular rotors--custom-designed molecules attached to a substrate via an axle about which the barrier to rotation is relatively low--and the investigation of their optical and mechanical properties. The dielectric response of molecular rotors possessing a permanent dipole moment, recently measured at frequencies in the kHz range, would be expected to be quite modest at optical frequencies. Nonpolar rotors, in contrast, could potentially exhibit large nonlinearities at optical frequencies, with the most promising rotor candidates being rigid molecules with molecular polarizabilities that are highly anisotropic; a good example is anthracene, for which the diagonal component of the polarizability tensor corresponding to the long axis of the molecule differs from that corresponding to axis normal to the ring plane by 20 Å3. Anthracene molecules are constrained to rotate about the principal axis associated with the diagonal component of the molecular polarizability that is intermediate in size. The rotation axes are oriented vertically ("azimuthal rotors") and are attached to a covalent monolayer grid such as that recently reported by Magnera et al. [in Nanostructural Materials: Clusters, Composites, and Thin Films, Moskovits and Shalaev, eds., ACS, 1997, p. 213]. In this configuration, the interaction between the incident laser beam and the induced rotor dipoles dominates the physics; rotor-rotor interactions are negligible. This allows us to calculate the nonlinear refractive index nI2 for the system, for which we obtain a relatively modest value of 2.6 × 10-15 cm2/W.
The development of stimulated emission from molecular transitions between vibrational energy levels of diatomic gases exposed to high intensity laser pulses through the Raman effect has been studied for many years. The energy levels are non-degenerate, the pump pulse is usually linearly polarized, and there are amenable classical models of the scattering. We have started a research program to study the development and gain of stimulated emission from molecular transitions between rotational energy levels in molecular hydrogen when exposed to a high intensity laser pulse. The rotational energy levels are necessarily degenerate in angular momentum and therefore the scattering is sensitive to the angular momentum of the pump light, i.e. its polarization. We present initial experimental verification of simplified classical theories for the polarization dependence of this type of scattering for the Stokes radiation and the Stokes--Anti-Stokes coupling common to all Raman scattering. Extensions of the classical theory to higher rotational orders and similarities and differences to stimulated vibrational Raman scattering and plans for further experiments are discussed. An exciting prospect is the prediction of generating coherent emission at the rotational Raman frequency itself by using an electric field perpendicular to the laser's direction of propagation.
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